JP6404147B2 - Crushing agent composition - Google Patents

Description

  The present invention relates to a crushing agent composition used for industrial crushing operations such as rocks and concrete structures. More specifically, the present invention relates to a crushing agent composition having reduced impact sensitivity, electrostatic sensitivity, and ignition sensitivity.

  Conventional crushing techniques in civil engineering works such as tunnel excavation work, land preparation work, road construction, and harbor construction include crushing methods using explosives, crushing methods using heavy construction machines, hydraulic rock drills, and the like.

  Although the explosive crushing method is very useful and economical, it requires a procedure for obtaining a consumption permit, and if there are private houses in the city or in the vicinity, it is instantaneous but high-level noise and ground vibration. Etc., and its use is greatly restricted.

  On the other hand, the crushing method using heavy construction machinery has a problem that it is relatively low level, but there are problems of continuous noise and vibration over a long period of time, and the work period is long due to poor work efficiency. Yes.

  As a method to compensate for these disadvantages, a method of crushing with a non-explosive crushing agent using the thermite reaction has attracted attention. As a non-explosive crushing agent composed of components not applicable to explosives under the Explosives Control Law, No. 3586356 discloses 100 parts by weight of a thermit agent comprising 30 to 2% by weight of ferric oxide, 83 to 10% by weight of cupric oxide and 30 to 15% by weight of aluminum powder, and 20 to 125 parts by weight. A non-explosive crushing agent having a particle size of ferric oxide of 0.15 to 1 μm is disclosed, and Japanese Patent No. 3688855 discloses aluminum and cupric oxide. Non-explosive crushing containing a thermite agent, a gas generating agent consisting of potassium alum or ammonium alum, a binder consisting of vinyl chloride, and a desensitizing agent consisting of calcium stearate Patent No. 4489142 discloses 35 to 45% by weight of metal oxide, 8 to 12% by weight of metal powder, sodium percarbonate, sodium azide, ammonium pentaborate tetrahydrate, Non-explosive crushing containing 42-55 wt% dissociation pressure agent such as magnesium sulfate heptahydrate, 0.5-5 wt% sulfur, 0.1-1.8 wt% binder such as methylcellulose Agents are disclosed.

Japanese Patent No. 3586356 Japanese Patent No. 3688855 Japanese Patent No. 4489142

  The purpose of the present invention is to exhibit a crushing effect equivalent to or better than that of conventional non-explosive crushing agents, and is excellent in safety during manufacturing and handling operations due to various sensitivity reductions. The purpose is to provide a non-explosive crushing agent that is not limited by the specified quantity in storage and handling.

  As a result of various studies from the viewpoint of ensuring safety and convenience during production and use, the present inventors have obtained metal oxides, metal powders and hydrates having a specific average particle size as the thermite agent. It has been found that the above-mentioned problems can be solved by defining the content ratio of the metal oxide and the metal powder together with the use of the metal oxide, and the present invention has been completed.

That is, the present invention
(1) a metal oxide having an average particle diameter of 0.1 to 30 μm, a metal powder having an average particle diameter of 20 to 60 μm, a hydrate having an average particle diameter of 0.5 to 5 mm, and a binder, The mass ratio of metal oxide / metal powder is 50/50 to 70/30, and includes a hydrate 20 to 50% by mass and a binder 0.1 to 5.0% by mass. object,
(2) The ratio of the average particle diameter of a metal oxide and a metal powder is metal oxide / metal powder = 1/2 to 1/20, The crushing agent composition according to (1),
(3) The crushing agent composition according to (1) or (2), wherein the metal oxide is cupric oxide, ferric oxide or a mixture thereof. (4) The metal powder is aluminum. The crushing agent composition according to any one of (1) to (3), which is magnesium or a mixture thereof,
(5) The hydrate is composed of aluminum sulfate · 18 hydrate, zinc sulfate · 7 hydrate, magnesium sulfate · 7 hydrate, potassium alum · 12 hydrate, and ammonium alum · 12 hydrate. The crushing agent composition according to any one of (1) to (4), which is one or more selected from the group,
(6) The crushing agent according to any one of (1) to (5), wherein the binder is at least one selected from the group consisting of ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and polyvinyl pyrrolidone. Composition,
About.

  According to the present invention, while maintaining the same or better crushing performance as conventional non-explosive crushing agents, it is easy to ensure safety during production and use by reducing various sensitivities, and it is not applicable to dangerous goods under the Fire Service Act, Storage and handling are possible without being limited by the specified quantity.

Hereinafter, the method of the present invention will be described in detail.
The present invention relates to a crushing agent in consideration of safety and convenience during manufacturing work and use.
The crushing agent of the present invention uses various metal oxides, metal powders, and hydrates having a specific average particle size, thereby reducing various sensitivities, increasing safety during production and use, and explosives. There is an advantage that it is not restricted by the Control Law and Fire Law.

  In the present invention, as the metal oxide, an oxidizing agent such as molybdenum trioxide, cupric oxide, manganese dioxide, potassium permanganate, ferric oxide, triiron tetroxide, calcium permanganate may be used. Preferably, cupric oxide, ferric oxide or a mixture thereof is used. The average particle diameter of the metal oxide used in the present invention is 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 5 to 15 μm. In the crushing agent composition of the present invention, the content of the metal oxide is preferably 25 to 55% by mass, more preferably 30 to 50% by mass, and particularly preferably 35 to 45% by mass. preferable. When the content of the metal oxide is within the above range, in particular, the impact sensitivity, the friction sensitivity, the electrostatic sensitivity and the ignition sensitivity are reduced, and a desired crushing performance is obtained.

  In the present invention, as the metal powder, any of zirconium, aluminum, titanium, magnesium, magnalium and the like that release high thermal energy by supplying oxygen from an oxidant can be used, preferably aluminum, Magnesium or a mixture thereof is used. The average particle diameter of the metal powder used in the present invention is 20 to 60 μm, preferably 30 to 60 μm, and more preferably 40 to 50 μm. If the average particle diameter of the metal powder is too small, there may be a problem in safety during manufacturing and handling due to an increase in various sensitivities. If the average particle diameter of the metal powder is too large, the desired gas pressure may be increased. It may not be obtained. When the average particle diameter of the metal powder is in the above range, impact sensitivity, electrostatic sensitivity and ignition sensitivity are reduced, and a desired generated gas pressure can be obtained. In the crushing agent composition of the present invention, the content of the metal powder is preferably 15 to 40% by mass, more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass. . When the content of the metal powder is within the above range, in particular, impact sensitivity, friction sensitivity, electrostatic sensitivity and ignition sensitivity are reduced, and desired crushing performance is obtained.

  The crushing agent composition of the present invention contains metal oxide / metal powder in a mass ratio of 50/50 to 70/30. The crushing agent composition of the present invention preferably contains metal oxide / metal powder in a mass ratio of 55/45 to 65/35. When the mass ratio of the metal oxide / metal powder is within the above range, impact sensitivity, friction sensitivity, electrostatic sensitivity and ignition sensitivity are reduced, and desired crushing performance is obtained.

  The crushing agent composition of the present invention contains the metal oxide having the above average particle size and the metal powder, but the ratio of the average particle size of the metal oxide to the metal powder is 1/2 to 1/20. Is preferable, and 1/5 to 1/10 is particularly preferable. When the ratio of the average particle diameter of the metal oxide and the metal powder is within the above range, in particular, impact sensitivity, friction sensitivity, electrostatic sensitivity and ignition sensitivity are reduced, and desired crushing performance is obtained.

  In the present invention, any hydrate can be used as long as the crystal water is instantly vaporized and released as a vapor by the high reaction heat generated by the thermite reaction between the metal oxide and the metal powder. However, aluminum sulfate · 18 hydrate, zinc sulfate · 7 hydrate, magnesium sulfate · 7 hydrate, potassium alum · 12 hydrate, and ammonium alum · 12 hydrate are preferably used.

  The crushing agent composition of this invention contains 20-50 mass% of hydrates with an average particle diameter of 0.5-5 mm. The crushing agent composition of the present invention preferably contains 30 to 40% by mass of a hydrate having an average particle diameter of 1 to 3 mm. When the average particle size and content of the hydrate are within the above ranges, impact sensitivity, friction sensitivity, electrostatic sensitivity and ignition sensitivity are reduced, and desired crushing performance is obtained.

  In the present invention, any binder can be used as long as it can bind a thermite agent composed of a metal oxide and a metal powder to the particle surface of the hydrate and maintain them at a constant component ratio. Preferably, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and polyvinyl pyrrolidone are used.

  The crushing agent composition of this invention contains 0.1-5.0 mass% binder. The crushing agent composition of the present invention preferably contains 0.3 to 3.0% by mass of a binder, and particularly preferably contains 0.5 to 1.0% by mass of a binder. When the hydrate content is within the above range, impact sensitivity, friction sensitivity, electrostatic sensitivity and ignition sensitivity are reduced, and desired crushing performance is obtained.

  In the present invention, the average particle size is a volume-based average particle size, and is defined as a 50% particle size in a volume-based cumulative particle size distribution by a laser diffraction / scattering method (microtrack method). Specifically, it is measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.).

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following examples,% indicates mass%.

Example 1
Cupric oxide (Nisshin Chemco Co., Ltd .: average particle size 0.9 μm) 38.2%, aluminum powder (Wako Pure Chemical Industries, Ltd .: average particle size 40 μm) 31.3%, magnesium sulfate 7 Hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: average particle size 0.8 mm) 30%, ethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5% previously dissolved in ethanol in a SUS container The mixture was mixed with a bamboo spatula, passed through a sieve having an opening of 2.8 mm, and then air-dried at room temperature all day to prepare a crushing agent composition.

(Example 2)
Cupric oxide (manufactured by Nippon Chemical Industry Co., Ltd .: average particle size 5 μm) 41.7%, aluminum powder (manufactured by Wako Pure Chemical Industries, Ltd .: average particle size 40 μm) 27.8%, ammonium alum 12 water 30% of Japanese product (Daimei Chemical Industry Co., Ltd .: average particle size 1.5 mm) and 0.5% of polyvinylpyrrolidone (Wako Pure Chemical Industries, Ltd.) 0.5% previously dissolved in acetone in a SUS container The mixture was passed through a sieve having a mesh size of 2.8 mm, and then air-dried at room temperature all day and night to prepare a crushing agent composition.
(Example 3)
Cupric oxide (Furukawa Chemicals Co., Ltd .: average particle size 5 μm) 35.2%, ferric oxide (JFE Steel Co., Ltd .: average particle size 1 μm) 3.5%, aluminum powder (Minalco Co., Ltd.) ) Manufactured: average particle diameter 25 μm) 20.8%, ammonium alum 12 hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: average particle diameter 0.8 mm) 40%, polyvinylpyrrolidone (Japanese sum) previously dissolved in ethanol After mixing with 0.5% of SUS container in a SUS container and passing through a sieve having an opening of 2.8 mm, the mixture was air-dried at room temperature for 24 hours to prepare a crushing agent composition.

(Comparative Example 1)
Cupric oxide (Nisshin Chemco Co., Ltd .: average particle size 0.9 μm) 43.6%, aluminum powder (Minalco Co., Ltd .: average particle size 5 μm) 10.9%, potassium alum 12 hydrate (Wako Pure Chemical Industries, Ltd .: average particle diameter 0.8 mm) 45%, ethyl cellulose (Wako Pure Chemical Industries, Ltd.) 0.5% previously dissolved in acetone was mixed with a bamboo spatula in a SUS container. Then, after passing through a sieve having an opening of 2.8 mm, it was air-dried at room temperature all day and night to prepare a crushing agent composition.

(Comparative Example 2)
Cupric oxide (manufactured by Nippon Chemical Industry Co., Ltd .: average particle size 5 μm) 43.6%, aluminum powder (manufactured by Wako Pure Chemical Industries, Ltd .: average particle size 25 μm) 10.9%, magnesium sulfate 7 water 45% of Japanese product (Wako Pure Chemical Industries, Ltd .: average particle size 0.8 mm) and 0.5% of methylcellulose (Wako Pure Chemical Industries, Ltd.) 0.5% dissolved in ethanol in advance in a SUS container The mixture was passed through a sieve having a mesh size of 2.8 mm, and then air-dried at room temperature all day and night to prepare a crushing agent composition.

(Comparative Example 3)
Cupric oxide (Furukawa Chemicals, Inc .: average particle size 5 μm) 54.2%, aluminum powder (Wako Pure Chemical Industries, Ltd .: average particle size 40 μm) 15.3%, potassium alum 12 hydrate 30% of the product (manufactured by Wako Pure Chemical Industries, Ltd .: average particle size 0.2 mm) and 0.5% of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) previously dissolved in ethanol in a SUS container The mixture was passed through a sieve having a mesh size of 2.8 mm, and then air-dried at room temperature all day and night to prepare a crushing agent composition.
(Comparative Example 4)
Cupric oxide (Dong Lin Metal Technology Co. Ltd .: average particle size 40 μm) 48.7%, aluminum powder (Minalco Co., Ltd .: average particle size 25 μm) 20.8%, ammonium alum 12 hydrate (Daimei Chemical Co., Ltd .: average particle size 1.5 mm) 30%, polyvinyl pyrrolidone (Wako Pure Chemical Industries, Ltd.) 0.5% previously dissolved in ethanol was mixed with a bamboo spatula in a SUS container. Then, after passing through a sieve having an opening of 2.8 mm, it was air-dried at room temperature all day and night to prepare a crushing agent composition.

  In the following manner, performance, stagnation sensitivity / friction sensitivity, electrostatic sensitivity, and small gas flame ignition sensitivity of the crushing agent compositions of Examples and Comparative Examples were confirmed.

(1) Performance (concrete crushing test)
In a concrete block 600 mm long and 800 mm high, each crushing agent is loaded into a charge hole with a minimum resistance line of 300 mm and a drilling length of 420 mm, ignited with a dedicated igniter, and the minimum dose at which the concrete block is crushed is measured. did.

(2) Drop sensitivity and friction sensitivity The drop sensitivity and the friction sensitivity were measured by the drop sensitivity test and the friction sensitivity test respectively defined in the pyrotechnic association ES-21 (1) and ES-22.

(3) Electrostatic sensitivity The electrostatic sensitivity was measured according to the electrostatic sensitivity test prescribed | regulated by the pyrotechnic association standard ES-25. Using an electrostatic sensitivity test device (manufactured by Nippon Technate Co., Ltd.), the sample state was measured in an open state, and the electrode gap length was 0.1 mm.

(4) Small gas flame ignition test A small gas flame ignition test, which is a judgment test for the second class of dangerous goods based on the Fire Service Act, was performed, and the time from when the flame contacted to ignition was measured. If the ignition time ≤ 3 seconds, the first-type flammable solid, 3 seconds <ignition time ≤ 10 seconds, the second-type flammable solid, non-ignition or non-continuous combustion will be non-dangerous. The designated quantities of the first type flammable solid and the second kind flammable solid are 100 kg and 500 kg, respectively. For storage and handling exceeding the designated quantity, permission at a specific place based on the Fire Service Act is required.
The test results are shown in Table 1.

  As is clear from the results of Table 1, in Comparative Example 1, the average particle diameter of the metal powder is small (5 μm), and the mass ratio of the metal oxide to the metal powder is large (the mass ratio of metal oxide / metal powder). 80/20), although exhibiting an excellent crushing effect, the electrostatic sensitivity is high, and the small gas flame ignition sensitivity is also high, which is a result corresponding to the second type combustible solid. On the other hand, in Examples 1 and 2 in which the average particle diameter of the metal powder is 40 μm and the mass ratio of the metal oxide / metal powder is 55/45 and 60/40, the electrostatic sensitivity is low and it is a non-hazardous material. At the same time, it was confirmed to have the same crushing performance as Comparative Example 1. In Example 3 where the average particle size of the metal powder was 25 μm and the mass ratio of metal oxide / metal powder was 65/35, good crushing performance and reduction in various sensitivities were confirmed. In Comparative Example 2, since the mass ratio of the metal oxide to the metal powder is large (the mass ratio of metal oxide / metal powder is 80/20), the sensitivity of falling is high, and other sensitivities are relatively insensitive. Although it was, it was confirmed that the crushing performance was relatively low. Furthermore, in Comparative Example 3, since the average particle diameter of the hydrate is small (0.2 mm) and the mass ratio of the metal oxide to the metal powder is large (the mass ratio of metal oxide / metal powder is 78/22). Although the sensitivity was low, the crushing performance was low. In Comparative Example 4, the average particle diameter of the metal oxide is large (40 μm) and exhibits excellent crushing effects, but the friction sensitivity and electrostatic sensitivity are high, and the small gas flame ignition sensitivity corresponds to the second kind of combustible solid. It was a result.

Claims (5)

A metal oxide comprising a metal oxide having an average particle diameter of 0.1 to 30 μm, a metal powder having an average particle diameter of 20 to 60 μm, a hydrate having an average particle diameter of 0.5 to 5 mm, and a binder. / mass ratio of the metal powder is 55 / 45-65 / 35, a hydrate 20-50 wt%, wherein the binder 0.1-5.0 wt%, an average particle diameter of the metal oxide and metal powder The ratio of metal oxide / metal powder = 1/2 to 1/20.   The crushing agent composition according to claim 1, wherein the metal oxide is cupric oxide, ferric oxide, or a mixture thereof.   The crushing agent composition according to claim 1 or 2, wherein the metal powder is aluminum, magnesium, or a mixture thereof.   The hydrate is selected from the group consisting of aluminum sulfate / 18 hydrate, zinc sulfate / 7 hydrate, magnesium sulfate / 7 hydrate, potassium alum / 12 hydrate, and ammonium alum / 12 hydrate The crushing agent composition according to any one of claims 1 to 3, wherein the composition is one or more kinds.   The crushing agent composition according to any one of claims 1 to 4, wherein the binder is at least one selected from the group consisting of ethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, and polyvinylpyrrolidone. object.